Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
  • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants

Definitions

• the invention relates to a method for producing crude oil, in which an aqueous surfactant formulation comprising at least one alkylpolyalkoxysulfate comprising propoxy groups and at least one further surfactant is injected through injection bores into an oil reservoir and the crude oil is removed from the deposit by production wells.
• an aqueous surfactant formulation comprising at least one alkylpolyalkoxysulfate comprising propoxy groups and at least one further surfactant is injected through injection bores into an oil reservoir and the crude oil is removed from the deposit by production wells.
• the process may be Winsor Type III microemulsion flooding.
• a deposit In natural oil deposits, petroleum is present in the cavities of porous reservoirs, which are closed to the earth's surface of impermeable cover layers.
• the cavities may be very fine cavities, capillaries, pores or the like. Fine pore necks, for example, have a diameter of only about 1 micron.
• a deposit In addition to crude oil, including natural gas, a deposit contains more or less saline water.
• the secondary funding is used.
• additional wells will be drilled into the oil-bearing formation in addition to the wells that serve to extract the oil, known as production wells.
• injection wells water is injected into the reservoir to maintain or increase the pressure.
• the oil is slowly pressed by the cavities in the formation starting from the injection hole in the direction of the production bore. But this works only as long as the cavities are completely filled with oil and the viscous oil is pushed through the water in front of him.
• the low-viscosity water breaks through cavities, it flows from this point on the path of the least resistance, ie through the channel formed and no longer pushes the oil in front of him.
• tertiary oil production It is known to further increase the oil yield by measures of tertiary oil production.
• An overview of tertiary oil production can be found, for example, in Journal of Petroleum Science and Engineering 19 (1998) 265-280 .
• For tertiary oil production include heat processes in which hot water or superheated steam is injected into the deposit. As a result, the viscosity of the oil is reduced.
• gases such as CO 2 or nitrogen can be used.
• surfactant flooding Surfactants which can reduce ⁇ to values of ⁇ 10 -2 mN / m (ultralow interfacial tension) are particularly suitable for this purpose. In this way, the oil droplets can be changed in shape and forced through the flood water through the capillary openings.
• the oil droplets can then combine to form a continuous oil bank. This has two advantages: Firstly, as the continuous oil bank progresses through new porous rock, the oil droplets located there merge with the bank. Furthermore, the oil-water interface is significantly reduced by the union of the oil drops to an oil bank and thus releases no longer needed surfactant. The released surfactant may then mobilize residual oil in the formation.
• Suitable surfactants for tertiary oil production should reduce the interfacial tension between water and oil (typically about 20 mN / m) to particularly low values of less than 10 - Reduce 2 mN / m to allow sufficient mobilization of the petroleum. This must be done at the usual storage temperature of about 15 ° C to about 130 ° C and in the presence of highly saline water, especially in the presence of high levels of calcium and / or magnesium ions; The surfactants must therefore be soluble in highly saline reservoir water.
• mixtures of surfactants have been frequently proposed, in particular mixtures of anionic and nonionic surfactants.
• the nonionic surfactants are polyethoxylated alkylphenols which have 6 to 20 ethoxy groups and whose alkyl radical has 5 to 20 C atoms or polyethoxylated aliphatic alcohols having 6 to 20 C atoms and 6 to 20 ethoxy groups.
• US 3,811,504 discloses a mixture of 2 different anionic surfactants and a nonionic surfactant for use in reservoirs whose reservoir water contains 0.15 to 1.2% calcium and magnesium ions.
• the first anionic surfactant is alkyl or alkylaryl sulfonates and the second is alkyl polyethoxysulfates.
• the nonionic surfactants may be polyethoxylated alkylphenols having 6 to 20 ethoxy groups and their alkyl group having 5 to 20 C atoms, or polyethoxylated aliphatic alcohols having 6 to 20 C atoms and 6 to 20 ethoxy groups.
• U.S. 4,077,471 discloses a surfactant mixture for use in a formation whose deposit water has a salt content of 7 to 22%.
• the mixture comprises a water-soluble alkylpolyalkoxyalkylsulfonate or alkylarylpolyalkoxyalkylsulfonate and a water-insoluble nonionic surfactant of an ethoxylated aliphatic alcohol or an ethoxylated, alkyl-substituted aromatic alcohol wherein the hydrocarbon groups each have 8 to 24 carbon atoms and the number of ethoxy groups is 1 to 20.
• US 4,293,428 discloses a petroleum production process in which surfactants of the general formula R- (PO) m (EO) n YM are injected into a petroleum formation, where R is an aliphatic hydrocarbon radical or an aliphatic substituted phenyl radical, PO is a propoxy group, EO is a Ethoxy group, Y for a sulfate, sulfonate, phosphate or carboxylate group, M for a cation and n and m each represent a number from 1 to 10.
• R is an aliphatic hydrocarbon radical or an aliphatic substituted phenyl radical
• PO is a propoxy group
• EO is a Ethoxy group
• Y for a sulfate, sulfonate, phosphate or carboxylate group
• M for a cation
• n and m each represent a number from 1 to 10.
• GB 2 168 095 A discloses a petroleum production process which involves injecting propoxylated surfactants of the general formula R- (PO) x -R'-SO 3 M or R- (PO) x OSO 3 M into a petroleum formation having a total salinity of from 20,000 ppm to 80,000 ppm ,
• R is an aliphatic or aliphatic-aromatic hydrocarbon radical having 10 to 20 carbon atoms
• x is a number from 2 to 15
• R ' is an alkylene group having 1 to 5 carbon atoms.
• the document contains no indications of the preparation or polydispersity of the surfactants.
• US 2006/0189486 A1 discloses the use of a mixture of at least one branched aliphatic anionic surfactant and an aliphatic nonionic surfactant for petroleum production.
• the branched aliphatic group preferably has 10 to 24 C atoms, and the degree of branching is 0.7 to 2.5
• WO 2009/050179 A1 discloses certain polyethersulfonates and their use for various purposes, including tertiary petroleum production.
• the polyethersulfonates include a hydrocarbon group having 6 to 30 carbon atoms.
• the polyethersulfonates can be combined with various ionic and nonionic surfactants.
• Winsor III microemulsion is in equilibrium with excess water and excess oil. Under these conditions of microemulsion formation, the surfactants occupy the oil-water interface and lower the interfacial tension ⁇ .
• Winsor III microemulsions are particularly low in viscosity compared to other types of emulsion, they can flood through the porous reservoir rock. By contrast, conventional emulsions can get stuck in the porous matrix and clog it up. Consequently, Winsor Type III microemulsion flooding is an extremely efficient process and, unlike an emulsion flooding process, requires significantly less surfactant.
• the surfactants are usually optionally injected together with cosolvents and / or basic salts (optionally in the presence of chelating agents). Subsequently, a solution of thickening polymer is injected for mobility control.
• Another variant is the injection of a mixture of thickening polymer and surfactants, cosolvents and / or basic salts (optionally with chelating agent) and subsequently a solution of thickening polymer for mobility control.
• These solutions should usually be clear to avoid blockage of the reservoir.
• the proportion of the microemulsion in the water microemulsion oil system should naturally be as large as possible at a defined amount of surfactant.
• the application parameters such as, for example, type, concentration and the mixing ratio of the surfactants used, are therefore adapted by the person skilled in the art to the prevailing conditions (temperature, salinity) in a given petroleum formation.
• the interfacial tension should be as low as possible and the separation into the phases of the microemulsion should be as fast as possible.
• the object of the invention was to provide surfactant mixtures which meet these requirements.
• the surfactants (A) have the general formula R 1 -O- (CH 2 -CH- (CH 3 ) O) x - (CH 2 -CH 2 O) y -SO 3 M (I).
• One or more different surfactants (A) of the formula (I) can be used.
• the radical R 1 is a straight-chain or branched, aliphatic and / or aromatic hydrocarbon radical having 8 to 32 carbon atoms, preferably 9 to 22, particularly preferably 9 to 18 and very particularly preferably 10 to 17 carbon atoms.
• It is preferably a straight-chain or branched aliphatic hydrocarbon radical, in particular a straight-chain or branched aliphatic hydrocarbon radical having 9 to 18 carbon atoms.
• a branched aliphatic hydrocarbon radical generally has a degree of branching of from 0.1 to 4.5, preferably from 1 to 3.5.
• degree of branching is defined here in a manner known in principle as the number of methyl groups in a molecule of the alcohol minus 1.
• the mean degree of branching is the statistical mean of the degrees of branching of all molecules of a sample.
• x represents a number of 4 to 30, preferably 6 to 18, and most preferably 7 to 14, and y represents a number of 0 to 30, preferably 0 to 20, and particularly preferably 0 to 10.
• M stands for H + or a k-valent counterion 1 / k Y k + .
• k stands for the charge of the counterion. It is preferably a monovalent counterion, such as NH 4 + -, ammonium ions with organic radicals or alkali metal ions.
• Y is Li + , Na + and K + , and particularly preferred is Na + .
• the surfactant (A) may be present as a free acid or as a salt thereof.
• R 1 is a linear, aliphatic hydrocarbon radical, in particular a linear, aliphatic hydrocarbon radical having 9 to 18 carbon atoms, where x is a number from 4 to 30, preferably 6 to 18.
• the surfactants (A) are prepared by means of an at least two-stage process by reacting in a first process step (1) an alcohol R 1 -OH with propylene oxide and optionally ethylene oxide to give an alkoxylated alcohol of the general formula R 1 -O- (CH 2 -CH - (CH 3 ) O) x - (CH 2 -CH 2 O) y -H (II) alkoxylated, wherein R 1 , x and y have the above meaning.
• the alkoxylated alcohols (II) are sulfated according to methods known in the art.
• the alkoxylation can be carried out using double metal cyanide (DMC) catalysts.
• DMC double metal cyanide
• alkoxylated alcohols are obtained which have a narrower molecular weight distribution than alkoxylated alcohols, which are obtained by means of a conventional base-catalyzed alkoxylation, for example a conventional alkoxylation with KOH.
• the molecular weight distribution of the resulting alcohols can be described in a manner known in principle by the so-called polydispersity D.
• D M w / M n is the quotient of the weight average molecular weight and the number average molar mass.
• DMC Doppler metal cyanide
• Suitable DMC catalysts are for example in the DE 102 43 361 A1 , in particular sections [0029] to [0041] and the literature cited therein, such as, for example WO 00/74845 or WO 99/16775 ,
• Zn-Co type catalysts can be used.
• the invention is not limited to the use of double metal cyanide catalysts for carrying out the alkoxylation.
• all methods are suitable in which the ratio Dv / D KOH ⁇ 1, where D v is the polydispersity of a product obtained by the method used and D KOH is the polydispersity of a product obtained by means of KOH catalysis.
• surfactants (A) as a catalyst for example, for example, Doppelhydroxidtone as in DE 43 25 237 A1 or catalysts selected from the group of hydrophobicized hydrotalcites, modified oxides or hydroxides of calcium, strontium or barium or phosphates of lanthanum or lanthanides.
• the formulation used comprises at least one different surfactant (B) of the general formula R 2 -Y (II).
• B the formulation used comprises at least one different surfactant of the general formula R 2 -Y (II).
• R 2 -Y II
• a mixture of several different surfactants (B) can be used.
• R 2 is a straight-chain or branched, aliphatic and / or aromatic hydrocarbon radical having 8 to 32 carbon atoms, preferably 9 to 28 and particularly preferably 10 to 24 carbon atoms.
• Y represents a hydrophilic group.
• these may be any desired hydrophilic groups, provided that the group is sufficiently polar to give the compound amphiphilic properties, ie surfactant properties. They may be nonionic surfactants, anionic, cationic or betainic surfactants.
• the group Y is a group selected from the group of sulfate groups, sulfonate groups, polyoxyalkylene groups, anionically modified polyoxyalkylene groups, glucoside groups, betaine groups or amine oxide groups.
• the surfactant (B) is a surfactant selected from the group of alkyl ethoxylates wherein the polyether group of the surfactant comprises each of 2 to 40 ether units.
• the surfactant (B) is a surfactant selected from the group of alkylbenzenesulfonates, olefin sulfonates or paraffin sulfonates.
• the formulation may optionally further comprise (A) and (B) different surfactants (C).
• Surfactants (C) may in particular be oligomeric or polymeric surfactants. Such polymeric cosurfactants can advantageously reduce the amount of surfactant required to form a microemulsion. Such polymeric cosurfactants are therefore also referred to as "microemulsion boosters".
• Examples of such polymeric surfactants (C) include amphiphilic block copolymers comprising at least one hydrophilic and at least one hydrophobic block. Examples include polypropylene oxide-polyethylene oxide block copolymers, polyisobutene-polyethylene oxide block copolymers and comb polymers having polyethylene oxide side chains and a hydrophobic backbone, wherein the backbone preferably comprises substantially olefins or (meth) acrylates as building blocks.
• the term "polyethylene oxide” is intended to include polyethylene oxide blocks comprising propylene oxide units as defined above. Further details of such surfactants are in WO 2006/131541 disclosed.
• a suitable aqueous formulation of the surfactants (A) and (B) and optionally (C) is injected through at least one injection well into the oil reservoir, and the deposit is withdrawn through at least one production well crude oil.
• Such a technique is also known as "surfactant flooding".
• the term "crude oil” in this context not meant pure-phase oil, but meant the usual crude oil-water emulsions.
• a deposit is provided with multiple injection wells and multiple production wells.
• the main effect of the surfactants lies in the reduction of the interfacial tension between water and oil. This increases the mobility of the petroleum in the reservoir, and thereby oil can be produced which would remain in the reservoir without the use of surfactants.
• the interfacial tension between water and oil should be lowered to values of less than 0.1 mN / m, preferably less than 0.01 mN / m.
• water can be injected into the formation (“water flooding”) to maintain the pressure, or preferably a higher-viscosity, aqueous solution of a polymer having a pronounced thickening effect (“polymer flooding”).
• water flooding aqueous solution of a polymer having a pronounced thickening effect
• Other known techniques are the injection of an aqueous solution containing surfactant and thickened polymer. Optionally, this can also contain alkali or soda. Subsequently, an aqueous solution containing only thickening polymer is injected.
• techniques are also known according to which the surfactants are first allowed to act on the formation. The person skilled in the details of the technical implementation of "Tensidflutens", “flooding” and “Polymer flooding” known and he applies depending on the nature of the deposit a corresponding technique.
• an aqueous formulation of the surfactants (A), (B) and optionally (C) is used.
• the formulations described below are particularly suitable for Winsor III microemulsion flooding, but can also be used for other techniques of surfactant flooding.
• the formulations may optionally also comprise water-miscible or at least water-dispersible organic solvents.
• Such additives serve in particular to stabilize the surfactant solution during storage or transport to the oil field.
• the amount of such additional solvents should as a rule not exceed 50% by weight, preferably 20% by weight and particularly preferably 10% by weight.
• only water is used to formulate.
• water-miscible solvents include in particular alcohols, such as methanol, ethanol or propanol, and C 1 to C 6 monoalkyl ethers of mono- or oligoglycols with up to 6 alkylene oxide units, such as butylethylene glycol, butyldiethylene glycol or butyltriethylene glycol.
• alcohols such as methanol, ethanol or propanol
• the weight ratio of the surfactants (A) and (B) to one another is from 10: 1 to 1:20, preferably from 3: 1 to 1:10 and most preferably from 2: 1 to 1: 4.
• the proportion of surfactants (A) and (B) together is at least 50% by weight with respect to the proportion of all surfactants present, ie the surfactants (A), (B) and optionally (C) together.
• the proportion is preferably at least 75% by weight, more preferably at least 90% by weight, and most preferably only surfactants (A) and (B) are used as surfactants in the formulation.
• the person skilled in the art can influence the optimum temperature for the formation of a microemulsion T opt by selecting the surfactants (A) and (B) and their weight ratio to one another and adapting them to the temperature of the deposit.
• the deposits in which the process is used have a temperature of at least 15 ° C, for example 15 to 130 ° C, preferably a temperature of 15 to 80 ° C and more preferably a temperature of 15 to 70 ° C.
• the total concentration of the surfactants in such a concentrate is 15 to 60% by weight, in particular 15 to 45% by weight.
• the surfactant mixtures used according to the invention with surfactants (A) prepared using double metal cyanide catalysts or double hydroxide clays have improved properties for tertiary mineral oil production. They lead in particular to particularly low interfacial tensions and to a particularly fast phase separation. Without wishing to be bound by any particular theory, on the one hand this seems to be due to a lower polydispersity of the surfactants (A).
• certain by-products such as Allylalkyoxysulfonate not or in comparison to the KOH catalysis smaller amounts to be present.
• Such products can be obtained by KOH-catalyzed rearrangement of propene oxide to allyl alcohol. The resulting allyl alcohol is then alkoxylated analogously to the alcohol R 1 - OH and sulfated.
• the products obtained are not effective as surfactants.
• the alcohol to be propoxylated (1.0 eq) is mixed with an aqueous KOH solution containing 50% by weight of KOH.
• the amount of KOH is 0.3 percent by weight of the product to be produced.
• the mixture is dehydrated at 100 ° C and 20 mbar for 2 h.
• the mixture is then flushed three times with N 2 , a pre-pressure of about 1.3 bar N 2 is set and the temperature is increased to 120-130 ° C.
• the propylene oxide is metered in so that the temperature remains between 125 ° C-140 ° C.
• the mixture is then stirred for 5 h at 125-140 ° C, rinsed with N 2 , cooled to 70 ° C and the reactor emptied.
• the amount of alkali hydroxide used is neutralized by means of acetic acid.
• the neutralization can be carried out with commercially available Mg silicates, which are then filtered off.
• the bright product is characterized by means of a 1 H-NMR spectrum in CDCl3, a gel permeation chromatography and an OH number determination and iodine color number, and the yield is determined.
• the alcohol to be propoxylated (1.0 eq) is mixed with a double metal cyanide catalyst (eg DMC catalyst from BASF Type Zn-Co) at 80 ° C.
• a double metal cyanide catalyst eg DMC catalyst from BASF Type Zn-Co
• DMC catalyst from BASF Type Zn-Co
• the amount of DMC is 0.1 percent by weight and less of the product to be produced.
• the mixture is then flushed three times with N 2 , a pre-pressure of about 1.3 bar N 2 is set and the temperature is increased to 120-130 ° C.
• the propylene oxide is metered in so that the temperature remains between 125 ° C-140 ° C.
• the bright product is characterized by means of a 1 H-NMR spectrum in CDCl3, a gel permeation chromatography and an OH number determination and iodine color number, and the yield is determined.
• the alkyl alkoxylate (1.0 eq) to be sulfated is dissolved in 1.5 times the amount of dichloromethane (on a weight percent basis) and cooled to 5-10 ° C. Thereafter, chlorosulfonic acid (1.1 eq) is added dropwise so that the temperature does not exceed 10 ° C.
• the mixture is allowed to warm to room temperature and stir for 4 h at this temperature under N 2 stream before the above reaction mixture into a half-volume aqueous NaOH solution at max. 15 ° C is dropped.
• the amount of NaOH is calculated so that there is a slight excess with respect to the chlorosulfonic acid used.
• the resulting pH is about 9-10.
• the dichloromethane is applied under a slight vacuum on a rotary evaporator at max. 50 ° C away.
• the product is characterized by 1 H-NMR and determines the water content of the solution (about 70%).
• alcohol description IC17 iso-C 17 H 35 -OH; Oxoalcohol, prepared by hydroformylation of iso-hexadecene, which is obtained by tetramerization of butene.
• the mean degree of branching of the alcohol is 3.1.
• the alcohol was propoxylated according to instructions 1 and 2, respectively.
• the respective degree of propoxylation is given in Table 1.
• the iC 17 propoxylate based on KOH catalysis contained 4% rearrangement product (allyl propoxylate) while the alkyl propoxylate based on DMC catalysis showed ⁇ 1% rearrangement product according to iodine color number and 1 H-NMR.
• both alkyl propoxylates were sulfated according to procedure 3.
• the degree of sulfation is according to 1 H-NMR in each case> 95%.
• Calibration substances were DIN polystyrene from PSS.
• the standard was toluene.
• Eluent was tetrahydrofuran for chromatography.
• the flow rate was 1 ml / min.
• Approximately 25 mg of the sample are dissolved in 1 ml of solvent (250 ml of THF-1.5 g of toluene), with the toluene already being mixed with the THF beforehand in order to achieve reproducible results.
• the interfacial tension between water and oil was determined in a known manner by measuring the solubilization parameter SP *.
• the determination of the interfacial tension via the determination of the solubilization parameter SP * is a method accepted in the art for the approximate determination of the interfacial tension.
• the solubilization parameter SP * indicates how much ml of oil per ml of surfactant used is dissolved in a microemulsion (Windsor type III).
• the interfacial tension ⁇ can be calculated from this by the approximate formula IFT ⁇ 0.3 / (SP *) 2 , if equal volumes of water and oil are used ( C. Huh, J. Coll. Interf. Sc., Vol. 71, no. 2 (1979 )).
• the formation of the microemulsion can be visually observed or with the help of Leümbos horren. It forms a three-phase system (upper phase oil, middle phase microemulsion, lower phase water). If the upper and lower phases are the same size and no longer change over a period of 12 h, then the optimum temperature (T opt ) of the microemulsion has been found. The volume of the middle phase is determined. From this volume, the volume of added surfactant is subtracted. The value obtained is then divided by two. This volume is now divided by the volume of added surfactant. The result is noted as SP *.
• the type of oil and water used to determine SP * is determined according to the system under investigation.
• petroleum itself can be used, or even a model oil such as decane or hexadecane.
• Both pure water and saline water can be used as water to better model the conditions in the oil formation.
• the composition of the aqueous phase may be adjusted according to the composition of a particular reservoir water.
• a 1 1 mixture of decane and a 6% NaCl solution was used.
• a surfactant mixture of 3 parts of each used Alkylpropoxysulfates (surfactant (A)) and 1 part of dodecylbenzenesulfonate (surfactant (B)) was added.
• the major surfactant concentration was 5% by weight of the water phase.
• Another surfactant (C) was used Butyldiethylenglykol (BDG).
• BDG Butyldiethylenglykol
• the cosurfactant concentration was 4% by weight of the water phase.
• Example 1 and Comparative Example 1 show that surfactants (A) prepared by DMC catalysis give lower interfacial tensions and faster microemulsion formation (lower separation time) than corresponding alkyl propoxy sulfates with equal numbers of propoxy units but alkoxylation under KOH catalysis. Table 1: Compilation of the results Example no.
• Surfactant (A) Surfactant (B) Weight ratio (A) / (B) Total amount (A) + (B) [wt.

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